Process of and composition for bleaching



Patented Oct. 13, 1928.

" U-NI TED 1 ST T S 3 P A' ENT WILLIAM B. STODDABD, .03 sa'antronn, CONNECTICUT,

OF NEW YORK, N. Y., ASSIGNORS TO PILOT LABORATOBY, INC., ARLINGTON,

AND vsm 'axoxa'rmm,

NEW JERSEY, A CORPORATION OF NEW JERSEY I monss on Ann comrosr 'rron, son nmncnme.

No Drawing. Application filed June aiaaa'seriai No.-197,22e.- Renewed a ta-19, 1927.

This invention relates to 'a process 0 and composition for bleachm organ c materi ls both animal and vegetab e such as flour an V other milling products, oil seedmeals, soaps, 5 waxes, oils, egg yolk, etc., and in its preferred embodiment relates more-particularly to a process of and composition, for bleaching such organic materials wherein there may be advanta eously employed organic 1 peroxids which eretofore have been considered too weak or too slow in their bleaching action for such use, or which normally have no bleaching action.

An important object of this invention is to make effective use in the bleaching art of inexpensive but normally inactive 'or relatively inactive organic peroxid's.

Another ob'ect of the invention is to make effective use in bleaching operations of substantially all of the available oxygen in or-' ganic per-oxidized compounds. A further object of the invention is to increase the rapidity of the bleaching action 5 of organic peroxid compounds;

secure the rapi bleaching of organic materials without over-bleachingthem whereby for example, the blue tone of over-bleached flour is avoided. I

A further object of the invention is to provide an organic peroxid bleaching composition which is more efiicient and e ective pound for pound than organic peroxids heretofore used or suggested for use as bleaching agents, whereby a materially smaller amount of bleaching material ma be employed to effect thorough bleaching than heretofore has been possible. A further object of the invention is to employing as an ingredient thereof an organic peroxid compound which is normally in a semi-solid or even liquid condition and accordngly normally unsuitable for use for bleaching-some organic materials, notably flour and other milling-products.

A further object of the invention is to increase the solubility of organic peroxid bleaching agents in vehicles, usually oils, in which coloring matters are dissolved as for example, the chromophoric oils of flour, seed meals and the like. By chromophoric oils,

we mean oils which contain coloring matter A further .ob'ect of the invention is to provide a substantially solid bleaching agent such-forexample as carotin, in solution'or SIIS6 8I1S1OII therein.

ther objects and advantages of the in'-'. -vent1onwil1- become apparent from the fol- 2 lowing description. I

Various or anic peroxid compounds here-- tofore have been proposed .-for use-in the bleachin ofcereals and other foodstuffs but many 0 them such as phthalyl peroxid,

cetyl peroxid, succinyl peroxid. or mixed peroxids such as benzo l-fumaryl peroxid and benzoyl-acetyl eroxid and the per-acids of the above,have een found to have ve small bleaching action per unit of them available oxygen. Therefore though capable of being manufactured economically and a higher percentage of available containingX an ,peroxids heretofore, used in oxygen t bleaching, such peroxide have found little or no application- 1n the bleaching art. We have discovered that inactive or relatively inactive organic peroxidized com'-.

which are constitutionally similar to some,

of the constituents of the material to be bleached. Thus for example, in blegching materials wherein the coloring matter is dissolved in"oil, a fattyacid peroxid and preferably a fatty acid peroxid or peroxidized compound produced by the peroxidation of a fat or oil, such-as cocoanut oil or the acids therefrom, may be advantageously added to an inactive or. relatively inactive organic peroxid compound and so used will act as an activator to increase its bleaching. action. j We also have found that the addition of an activat'ng organic peroxid compound. to an inactive or relatively inactive organic peroxid, aside from actlng on the inactive peroxid compound to assist or activate it in giving up its oxygen also, in the case of oil insoluble organicperoxids, brings about a solution of theinactive per-compound in the chromophoric oilcontained in the material to be bleached. In a case where the coloring matter to be bleached is dissolved in a chromophoric oil it will readily be seen that the solubility of a bleaching peroxid in the chroinophoric oil of the materials to be bleached,

sflsuilffate, starch l 'the'n ready for use as a bleaching agent.

brings about a condition of maximum bleaching effect, because of the intimac of contact. For this reason, the solubility of a bleaching peroxid in oil has a direct relat on to the bleaching power. Thus an activating peroxid-which itself is oil soluble, not only activates the inactive or relatively inactive peroxids but solubilizes them in the oil or oily constituents in which such -i nact1ve peroxy compounds are normally Insoluble or relatively insoluble.

In the production of our improved bleaching composition we may advantageously proceed as follows:

In a suitable vessel fitted wlth any deslred means of vigorous agitation are placed 225 liters of 7 per cent. hydrogen peroxid. This is then diluted by adding about 200 liters of water. To this solution is then added 246 kilograms of sal soda. The mixture is then agitated'and cooled to about 5 C. To this solution while being vigorously agitated is gradually added within about minutes a mixture of 87.5 kilograms of a mixture of'two gram moles of benzoyl chlorid and one gram mole of fumaryl chlorid and 12.5 kilograms of any fatty acid chlor1d, preferably a chlorid-of a soap forming fatty acid, e.g., capryl chlorid, lauryl chlorld, oleyl chlorid- During this addition the tem perat-ure is held as near 0 C. as possible. The mass is agitated until the odor of the acid chlorids disappears. This ordinarily requires from 10 to minutes. Upon the completion of the reaction the mixture of peroxids formed is filtered, washed with water, dried with or without the addltlon of inert fillers, e. g., calcium sulfate, magnesium or the like and ground. It is It is to be understood that the details of procedure, the temperature limits, ingredients and proportions of ingredients may be widely varied as will be obvious to anyone skilled in the art. Thus in a modified process of producing our bleaching composition we add a mixture of benzoyl chlorid and fatty acid chlorid or chlorids to other chlorids, as for example benzoyl and fumaryl chlorids, or to succinyl, phthalyl or citryl chlorid and then carry out the peroxidation of the mixed chlorids as described above. Instead of using a single fatty acid chlorid with other organic acid chlorid or chlorids in the peroxidation step we may use a mixture of two or more fatty acid chlorids.

We also may produce our bleaching composition by intimately ,mixi'ng an active organic peroxidized compound preferably but not necessarily, a fatty acid peroxid or a mixture of fatty acid peroxids, in suitable proportions with the organic peroxy compounds to be activated, which in the most advantageous practice of our process will be an inactive,-nonbleaching or a relatively of the resu ting peroxy compounds are widely" changed. Thus some of the eroxid compounds are solid, some oily sollds and some even oils. This is perhaps due to eutectic mixtures formed. In the practice of our process we may employ these liquid or semiliquid organic peroxids in admixture with activating organic per compounds, such for example as the peroxide or per acids of fatty acids, notably peroxids of the higher or so-called soap forming fatty acids.

Although in the illustrative example given above we have used as an activating peroxid a peroxid of a so-called soap forming fatty acid it is to be understood that fatty acids other than the higher fatty acids or so-called soap forming fatty acids may be used. For example, in place of the capryl peroxid, lauryl peroxid, or oleyl peroxid or mixtures thereof, we may employ as the activating peroxid, crotonic acid peroxid and valeric acid peroxid or mixtures thereof.

Ne also may use as the activating peroxids, 'peroxids of non-fatty acids such for example, as benzoyl. peroxid, cinnamic acid peroxid, phenylacetyl peroxid, or mixtures thereof. In using activating organic peroxids with relatively inactive organic peroxide we. have found that satisfactory and highly economical results are obtained by mixing with the relatively inactive peroxid from 5 to 10 per cent by weight of the activating peroxid and in the employment of such mixture we have found that we may advantageously employ from one-half to one-sixth of the quantity of bleaching agent commonly employed when using other organic peroxids, such for example, as benzoyl peroxid in the bleaching operation.

Even a somewhat active peroxid like benzoyl peroxid or its homologues, can be further activated when intimately mixed with about 510per cent of a fatty acid peroxid such for example as butyric acid peroxid, caproic acid peroxid or capric acid peroxid. When so activated an amount of peroxid composition equivalent to about .004 per cent by weight of the flour or other material to be bleached is enough to give a bleaching effect equal to that produced by using .025 per cent by weight of the unactivated benzoyl peroxid.

We also may employ as the activating agent a per-compound of an inorganic material such as calcium peroxid, sodium peroxid, ammonium per-sulphate, sodium chlorate and other per-compounds.

In its broadest aspect our invention involves the use of any activating per-compound to activate any other less active orably used in higher proportions as or exganic peroxid whereby the bleaching action of the less active perioxid is enhanced.

We have found that we may employ as low as 1 or 2 per cent of the activating percompound, as for example, a fatt acid peroxid such as those above referre to, in admixture with a sluggish or less active organic peroxid such for example, as phthalyl or fumaryl peroxid, and obtain a bl eaching agent having greatly enhanced efliciency. By increasing the proportion of the activator peroxid to about 15 per cent of the mixture, in the case where a peroxid of a fatty acid is employed, the resulting product has still greater bleaching efiiciency. For example, one pound of such mixed peroxid compound intimately mixed with 30,000 pounds of flour and allowed to stand at ordinary atmospheric temperatures for 48 hours, produces remarkably rapid, effective and torough bleachin and there is little tendency to produce t e undesired blue. tone frequently caused b overbleaching with other organic peroxid bleaching compositions. It should be noted that some activator peroxids such as the fatty acid peroxids, need to be used only in the proportion of from 1 to 2 per cent. of the weight of the inactive or less active peroxids. Other activating peroxids than the fatty acid .peroxlids are referample, in proportions of from 5 to 20 per cent by weight of the peroxid to be activated. Each activator peroxy compound has certain definite proportions to give optimum activating effect with each individual in; active or less active peroxy compound. These proportions, as is evident, must necessarily vary between Wide limits, dependmg upon the nature of the activator peroxid, that of the peroxy compound to be activated and the materials to be bleached but in all cases which we have investigated the addition of the activating peroxid in the proportion of from 5 to 10 per cent by weight of the less active peroxid has given satisfactory and economical results.

We have found that the fatty acid per compounds preferably peroxids made'bythe peroxidation of soap forming fatty acids or from organic acids which occur in natural fats and oils, not only have pronounced} bleaching action. but possess marked activating influence upon less active, inactive or sluggish organic peroxids or per-compounds. We have obtained particularly satisfactory results by the use of the peroxidized higher fatty acids notably caproic, oleic, and the like.

The fatty acid per-compounds are particularly advantageous for use as activators in in our improved bleaching compositionsby reason of their peculiar quality of rendering other organic per-compounds normally insoluble in the -color,carrying oils of organic matters, soluble. in suchoils, whereby the bleachin of oils and organic materials whose o1 y content contains coloring matter mifi be rapidly and satisfactorily effected.

y the term inactive organic eroxids we refer to those per-compoun s whose available oxygen content is not readily given up in the bleachin operation and which are normall inefiectlve in bleachin organic materia swhen merely intimate y mixed therewith. The terms peroxid, per-com: pound, peroxy com ound, peroxidized compound, etc., as use herein include organic peroxids, per-acids, per-acid salts and like per-compounds.

Many of the inactive or relatively inactive t pesof organic peroxids contain more availa is oxygen than the benzoyl peroxid heretofore used in bleaching flour and other food stuffs and are more economical to make. Acetyl, fumaryl and succinyl peroxids for example, contain more than twice as much available oxygen as benzoyl peroxid. Such inactive or relatively inactlve peroxids could not be made available for bleaching organic materials without the use of an actlvator.

While our invention is intended primarily for making use as bleaching agents of organic peroxid compoundswhich are inactive or relatively inactive in bleaching and particularly such peroxids as have a high content of available oxygen, it will be understood that our invention is adapted to be successfully employed in connection with other organic peroxy bleaching agents whereby, by the use 'of an activating peroxidized compound as hereinbefore set forth, such organic peroxids act more rapidly and eflectively in bleaching than when used without the employment of the activating organic peroxid therewith.

' This application is a continuation in artof our application Serial No; 177,218, ed March 21, 1927, for process of and composition for bleaching'with certain additional subject matter embodied therein.

While we have described in detail the preferred practice of our invention and the preferred proportions of ingredients. it is to be understood that our invention is not limited thereto nor otherwise than as set forth in the subjoined claims.

We claim:

1. A process of bleaching comprising subjecting the material to be bleached to the action of an organic peroxid compound and an activating per-'compound' therefor, whereby the effectiveness of the bleaching action of the organic peroxid compound is increased.

2. A process of bleaching comprising subjecting the material to be bleached to the action of an organic peroxid compound and an activating organic peroxid therefor,

whereby the effectiveness of the bleaching action of the first organic peroxid compound is increased.

3. A process of bleaching comprising sub jecting the material to be bleached to the action of a normally relatively inactive organic peroxid compound and an active organic per-compound, the active organic per-compound being an activator for the relatively inactive organic peroxid compound in the blcachin operation.

4-. A process of bleac ing which comprises subjecting -he material to be bleached to the action of a normally relatively inactive organic peroxid, and an activating peroxid therefor, which activating peroxid comprises a fatty acid peroxid.

5. A process of bleaching comprising subjccting a solid material to be bleached to the action of a normally nonsolid relatively inactive organic peroxid compound and, a solid organic peroxid in such proportions as to produce a solid mixture, one of said peroxid compounds being an active bleaching agent.

6. A process of bleaching comprising subjecting a chromophoric oil containing material to be bleached to the action of an organic peroxid which is insoluble in said oil and an organic peroxid which is soluble in said oil.

7. A process of bleaching comprising subjecting a chromophoric oil containing material to be bleached to the action of a relatively inactive organic peroxid compound which is insoluble in said oil and a peroxidized acid occurring in natural fats and oils which peroxid is soluble in said oil.

8. A process of bleaching comprising subjecting the material to be bleached to the action of a normally relatively inactive organic per-compound and a peroxid of an acid of the type occurring in animal and vegetable fats and oils.

9. A process of bleaching comprising sub- 7 chromophoric Oll containing met-- jecting a terial to be bleached, to the action of a relatively inactive organic peroxid and a higher fatty acid peroxid compound which is soluble in said oil.

10. A process of bleaching comprising subJecting a chromophoric 011 containing .compound which is insoluble in the oil of the material to be bleached, and an active organic peroxid which is soluble in said oil.

14. A bleaching agent comprising a relatively inactive organic peroxld which is insoluble in the oil of the material to be bleached, and an organic eroxid compound which is soluble in said oif.

15. A bleaching agent comprising a normally oil insoluble relatively inactive oganic peroxid and an oil soluble; active organic peroxy compound.

16. A bleaching agent comprising a relatively inactive nonsolid organic peroxid compound and a solid active organic eroxid.

17. A bleaching agent comprising a relatively inactive organic peroxid and a fatty acid peroxid compound.

18. A bleaching agent comprising a normally inactive organic peroxid and peroxy compound of acids of the type occurring in animal and vegetable fats and oils.

19. A bleaching agent comprising a normally relatively inactive organic peroxid compound which is insoluble in the oil of the material to be bleached, and an activator therefor comprising a fatty acid peroxid which is soluble in said oil.

In testimony whereof we afiix our signatures.

WILLIAM B. STODDARD. VAMAN R. KOKATNUR.

per-03y compound which is 

